CN101538386B - Agricultural polyethylene resin composition - Google Patents

Agricultural polyethylene resin composition Download PDF

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Publication number
CN101538386B
CN101538386B CN200810102245XA CN200810102245A CN101538386B CN 101538386 B CN101538386 B CN 101538386B CN 200810102245X A CN200810102245X A CN 200810102245XA CN 200810102245 A CN200810102245 A CN 200810102245A CN 101538386 B CN101538386 B CN 101538386B
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peroxide
lldpe
linear low
density polyethylene
resin composition
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CN101538386A (en
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魏福庆
许惠芳
王卓妮
刘义
陈基堂
竺栋荣
邓守军
李朋朋
段宏义
殷茜
乔彤森
张庆国
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China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

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Abstract

The invention discloses an agricultural polyethylene resin composition. The composition mainly consists of linear low-density polyethylene LLDPE and organic peroxide, wherein the organic peroxide is combined by di-tert-butyl peroxide DTBP and tert-butyl hydroperoxide TBHP according to the combination ratio of between 1:1 and 6:1, and the consumption of the organic peroxide is between 500 and 2,500ppm (based on each gram of linear low-density polyethylene). In the composition, the linear low-density polyethylene LLDPE is cross-linked by compounding the peroxide, and when the obtained modified high-bath strength LLDPE resin is used for blowing a 80 mum agricultural green house membrane, and under the condition of ensuring the membrane blowing stability and the quality of the membrane, the consumption of the peroxide is lowered, so that the production cost is also lowered.

Description

A kind of agricultural polyethylene resin composition
Technical field
The present invention relates to a kind of agricultural polyethylene resin composition, be specifically related to a kind of linear low density polyethylene (LLDPE) resin combination of modification.
Background technology
Linear low density polyethylene (LLDPE) is the novel polyethylene that grows up the latter stage seventies, (LDPE) compares with high-pressure polyethylene, its production equipment less investment, production cost is low, and all is better than the latter in all many-sides such as physical strength, elongation, resisting environmental stress and cracking, paracentesis resistance and tear strengths.Therefore, in the last thirty years, the LLDPE tempo is very fast, almost is penetrated into all traditional markets of polyethylene (PE) at present, comprises film, tubing, electric wire, hollow piece and tun etc.But because LLDPE self melt strength is little, drawdown is big, and bubble stability is poor in blowfilm shaping processing, and parison is difficult for, and has therefore limited its application percentage in high-strength thin-film.Utilize organo-peroxide and LLDPE that crosslinking reaction takes place and improve the LLDPE melt strength, thereby the processibility of improving LLDPE is a feasible technological line.CN1566192A discloses a kind of agricultural polyethylene resin composition, mainly form by linear low density polyethylene and ditertiary butyl peroxide, wherein the consumption of ditertiary butyl peroxide is 3000～6000ppm (is benchmark with the linear low density polyethylene), and the mode of extruding by twin screw can obtain said composition.This resin combination can be used to blow the agriculture greenhouse film of 80 μ m.But the large usage quantity that problem is an organo-peroxide that said composition exists not only makes production cost raise, and be easy to generate too much gel in the course of processing, makes the film flake more, influences its use properties.
Summary of the invention
The present invention is by preferred composite use organo-peroxide, and discovery can effectively reduce the consumption of organo-peroxide in linear low density polyethylene, and improves the processing characteristics of resin.
Agricultural polyethylene resin composition of the present invention mainly is made up of linear low density polyethylene (LLDPE) and organo-peroxide, wherein organo-peroxide is by ditertiary butyl peroxide (DTBP) and composite the forming of tertbutyl peroxide (TBHP), compound proportion is 1: 1 to 6: 1, and its consumption is 500～2500ppm (is benchmark with every gram linear low density polyethylene).The used linear low density polyethylene of the present invention (LLDPE) is a powdered resin, and water ratio is lower than 500ppm/g, tap density 0.35～0.50g/cm 3(measuring) according to GB/T 16913.3-1997, melt flow rate (MFR) 0.5～3.0g/10min (measuring) according to GB/T 3682, weight-average molecular weight is 7～130,000, number-average molecular weight is 2.5～3.0.The present invention can add other resin treatment auxiliary agent arbitrarily, as oxidation inhibitor, slipping agent, opening agent etc.
Agricultural polyethylene resin composition of the present invention can pass through Banbury mixer, kneader, forcing machine preparation, prepared in twin-screw extruder best results wherein, tool commercial production conditions.
The present invention carries out crosslinked by composite superoxide to linear low density polyethylene (LLDPE), blow the agriculture greenhouse film of 80 μ m with resulting modification high fondant-strength LLDPE resin, under the prerequisite that guarantees blown film stability and film quality, reduce the consumption of superoxide, thereby reduced production cost.
Embodiment
Φ 34 twin screw extruders of producing with German Lestreiz company are reactor, and after LLDPE resin and superoxide, oxidation inhibitor were mixed in the mixed device of height, extruding pelletization obtained modification LLDPE resin.Concrete composition of raw materials and modification LLDPE basis rerum natura sees Table 1, table 2.
DFDA7042: Lanzhou Petrochemical Company product, density 0.918g/cm 3, melt flow rate (MFR) 2.0g/10min;
LL101AA: Lanzhou Petrochemical Company product, density 0.918g/cm 3, melt flow rate (MFR) 1.0g/10min;
Oxidation inhibitor: composite antioxidant B561, Yingkou scene chemical industry company limited product;
Organo-peroxide: ditertiary butyl peroxide (DTBP) tertbutyl peroxide (TBHP) and benzoyl peroxide (BPO) are auxiliary reagent factory, Lanzhou product.
Table 1 composition of raw materials
Numbering Base resin DTBP+TBHP /ppm DTBP and TBHP mass ratio Oxidation inhibitor/ppm
Embodiment 1 DFDA7042 500 4∶1 2000
Embodiment 2 DFDA7042 1000 4∶1 2000
Embodiment 3 DFDA7042 1500 4∶1 2000
Embodiment 4 DFDA7042 2000 4∶1 2000
Embodiment 5 DFDA7042 2500 4∶1 2000
Embodiment 6 DFDA7042 3000 4∶1 2000
Embodiment 7 LL101AA 1500 1∶2 2000
Embodiment 8 LL101AA 1500 1∶1 2000
Embodiment 9 LL101AA 1500 4∶1 2000
Embodiment 10 LL101AA 1500 6∶1 2000
Embodiment 11 LL101AA 1500 7∶1 2000
Comparative Examples 1 LL101AA 1500 4: 1 (DTBP and BPO mass ratio) 2000
Comparative Examples 2 LL101AA 1500 4: 1 (BPO and TBHP mass ratio) 2000
Comparative Examples 3 DFDA7042 250 4∶1 2000
Table 2 modification LLDPE resin property
Numbering Base resin Melt flow rate (MFR)/(g/10min) Melt flow ratio Melt strength/cN
Embodiment 1 DFDA7042 1.54 42.5 3.24
Embodiment 2 DFDA7042 1.26 51.3 3.52
Embodiment 3 DFDA7042 0.98 63.8 3.69
Embodiment 4 DFDA7042 0.64 70.2 3.81
Embodiment 5 DFDA7042 0.43 75.9 3.97
Embodiment 6 DFDA7042 0.33 81.4 4.26
Embodiment 7 LL101AA 0.43 80.7 3.54
Embodiment 8 LL101AA 0.45 82.1 4.06
Embodiment 9 LL101AA 0.46 82.4 4.23
Embodiment 10 LL101AA 0.42 80.2 4.02
Embodiment 11 LL101AA 0.40 78.5 3.95
Comparative Examples 1 LL101AA 0.55 70.3 3.52
Comparative Examples 2 LL101AA 0.61 72.4 3.46
Comparative Examples 3 DFDA7042 1.76 37.1 2.72
At 190 ℃ of following blown films, its complete processing and product performance see Table 3, table 4 with above-mentioned modified resin.
Table 3 film-blowing process and bubble stability
Numbering Screw speed/rpm Main frame electric current/A Pulling speed/(m/min) Thickness/μ m Blow-up ratio Processing stability
Embodiment 1 50 8.0 9.0 80 2.5 The film bubble is more stable
Embodiment 2 50 7.8 9.0 80 2.5 The film bubble is stable
Embodiment 3 50 7.8 9.0 80 2.5 The film bubble is stable
Embodiment 4 50 7.5 9.0 80 2.5 The film bubble is stable
Embodiment 5 50 7.5 9.0 80 2.5 The film bubble is stable
Embodiment 6 50 7.6 9.0 80 2.5 The film bubble is stable, flake is more
Embodiment 7 50 7.5 9.0 80 2.5 The film bubble is unstable
Embodiment 8 50 7.8 9.0 80 2.5 The film bubble is more stable
Embodiment 9 50 7.6 9.0 80 2.5 The film bubble is stable
Embodiment 10 50 7.7 9.0 80 2.5 The film bubble is stable, and flake is on the high side
Embodiment 11 50 7.6 9.0 80 2.5 The film bubble is stable, the fish clothes are more
Comparative Examples 1 50 7.8 9.0 80 2.5 The film bubble is unstable
Comparative Examples 2 50 7.9 9.0 80 2.5 The film bubble is unstable
Comparative Examples 3 50 8.2 9.0 80 2.5 Unstable, the easily broken film of film bubble
The contrast of table 4 film rerum natura
Figure S200810102245XD00041

Claims (1)

1. agricultural polyethylene resin composition, mainly form by linear low density polyethylene LLDPE and organo-peroxide, it is characterized in that described organo-peroxide is ditertiary butyl peroxide DTBP and tertbutyl peroxide TBHP is composite forms, its consumption is 500～2500ppm, with every gram linear low density polyethylene is benchmark, and ditertiary butyl peroxide DTBP and tertbutyl peroxide TBHP compound proportion are 1: 1 to 6: 1.
CN200810102245XA 2008-03-19 2008-03-19 Agricultural polyethylene resin composition Active CN101538386B (en)

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CN101538386B true CN101538386B (en) 2011-06-22

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167855B (en) * 2010-02-25 2012-10-17 中国石油天然气股份有限公司 Metallocene polyethylene greenhouse film resin composition
CN101824178A (en) * 2010-04-06 2010-09-08 湖北众联塑业有限公司 Method for reducing flow rate of polyethylene melt
CN102408615B (en) * 2010-09-21 2013-04-24 中国石油天然气股份有限公司 Polyethylene geomembrane resin composition and preparation method thereof
CN102408600B (en) * 2010-09-21 2013-04-24 中国石油天然气股份有限公司 Metallocene polyethylene greenhouse film resin composition with high intensity and ultra-broad width, and its preparation method
CN102408616B (en) * 2010-09-21 2013-04-24 中国石油天然气股份有限公司 Over-wide polyethylene greenhouse film resin composition and preparation method thereof
CN102408613B (en) * 2010-09-21 2013-04-24 中国石油天然气股份有限公司 Polyethylene heavy packaging film resin composition and preparation method thereof
CN102408601B (en) * 2010-09-21 2013-02-13 中国石油天然气股份有限公司 Super-wide-breadth metallocene polyethylene greenhouse film resin composition and preparation method thereof
CN102408614B (en) * 2010-09-21 2013-04-24 中国石油天然气股份有限公司 Polyethylene greenhouse film resin composition with high intensity and ultra-broad width, and its preparation method
CN102863670B (en) * 2011-07-08 2014-06-04 中国石油天然气股份有限公司 Preparation method of special coating resin composition for polyethylene
CN102952310B (en) * 2011-08-19 2015-05-27 中国石油天然气股份有限公司 Metallocene polyethylene agricultural film resin composition and its preparation method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1218066A (en) * 1997-11-13 1999-06-02 中国石油化工总公司 Resin composition for extrusion blow moulding
JP2003238756A (en) * 2002-02-18 2003-08-27 Kuraray Co Ltd Thermoplastic polymer composition having gas-barrier properties
CN1566192A (en) * 2003-06-18 2005-01-19 中国石油天然气股份有限公司 Agricultural polyethylene resin composition
WO2005063896A2 (en) * 2003-12-24 2005-07-14 Dow Global Technologies Inc. Free-radical-initiated crosslinking of polymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1218066A (en) * 1997-11-13 1999-06-02 中国石油化工总公司 Resin composition for extrusion blow moulding
JP2003238756A (en) * 2002-02-18 2003-08-27 Kuraray Co Ltd Thermoplastic polymer composition having gas-barrier properties
CN1566192A (en) * 2003-06-18 2005-01-19 中国石油天然气股份有限公司 Agricultural polyethylene resin composition
WO2005063896A2 (en) * 2003-12-24 2005-07-14 Dow Global Technologies Inc. Free-radical-initiated crosslinking of polymers

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